DE102005053019A1 - Comb polymers and their use as additives for preparations of mineral binders - Google Patents

Abstract

The present invention relates to new comb polymers which have on a carbon backbone poly-C¶2¶-C¶4¶-alkylene ether side chains A and functional groups B, which are in the form of anionic groups at pH> 12, as well as the salts of such comb polymers . The invention also relates to the use of these comb polymers as additives in preparations which contain a mineral binder. The polyalkylene ether side chains A have the following formula: DOLLAR A * -U- (C (O)) ¶k¶-X- (Alk-O) ¶n¶-YZ A DOLLAR A where DOLLAR A * is the binding site to the Indicates carbon backbone of the comb polymer, DOLLAR AU stands for a chemical bond or an alkylene group with 1 to 8 carbon atoms, DOLLAR AX is oxygen or a group NR, DOLLAR A k is 0 or 1, DOLLAR A n is an integer whose Average value, based on the comb polymer, is in the range from 5 to 300, DOLLAR A Alk stands for C¶2¶-C¶4¶-alkylene, whereby Alk within the group (Alk-O) ¶n¶ can be the same or different, DOLLAR AY stands for a linear or branched alkylene group with 2 to 8 carbon atoms, which can carry a phenyl ring, DOLLAR AZ stands for a nitrogen-bonded 5- to 10-membered nitrogen heterocycle which, as ring members, next to the nitrogen atom and next to carbon atoms, 1, 2 or 3 additional heteroatoms selected from oxygen, nitrogen and sulfur can sen, whereby the ...

Description

The present invention relates to novel comb polymers which carry on a carbon backbone poly-C ₂ -C ₄ -alkylene ether side chains A and functional groups B, which are present at pH> 12 in the form of anionic groups, and the salts of such comb polymers. The invention also relates to the use of these comb polymers as additives in preparations of mineral binders.

Comb polymers having a carbon backbone bearing poly-C ₂ -C ₄ alkylene ether side chains and anionic groups, especially carboxylate groups, are useful as additives for mineral binders and binders, especially for cement and cementitious binders such as mortars, cementitious plasters, and especially for concrete , but also for gypsum and plaster-based binding materials such as model, stucco or plaster, plaster, gypsum, etc. Use.

you Assumes that the comb polymers are the particles of the mineral binder in the ready-to-use preparation of the binder, d. H. one with water prepared preparation, and disperse that dispersing Effect of Kammpolymere a liquefaction of the ready to use Preparations effected. Thus, to set a specific Working viscosity ready-to-use preparation when mixing less water, based on the mineral binder, needed as in a non-additive Preparation, resulting in an increased Ultimate strength of the additive preparation in the set condition results. Conversely, additivierte preparations have the same Amount of water, based on the mineral binder, a reduced viscosity as non-additive preparations, which for many purposes such as Cast concrete or screed desired is.

EP-A 331 308 describes comb polymers for the dispersion of cement, which contain in copolymerized form a monoethylenically unsaturated carboxylic acid, a monoethylenically unsaturated sulfonic acid and an ester of a poly-C ₂ -C ₃ -alkylene glycol mono-C ₁ -C ₃ -alkyl ether.

EP-A 560 602, in turn, describes the use of comb polymers which comprise an alkenyl ether of a poly-C ₂ -C ₁₈ -alkylene glycol mono-C ₁ -C ₄ -alkyl ether and maleic acid or maleic anhydride in copolymerized form as additives for concrete.

EP-A 753 488, in turn, discloses the use of comb polymers which contain monoethylenically unsaturated carboxylic acids and esters of monoethylenically unsaturated carboxylic acids of polyoxy-C ₂ -C ₄ -alkylene mono-C ₁ -C ₄ -alkyl ethers in copolymerized form and which have a specific molecular weight distribution. known as a dispersant for cement. Similar polymers are described for this purpose in EP-A 792 850.

EP-A 725 044, in turn, describes the use of comb polymers of monoethylenically unsaturated monocarboxylic acids and esters of monoethylenically unsaturated carboxylic acids with polyoxyethylene mono-C ₁ -C ₅ -alkyl ethers in hydraulically setting compositions based on a mixture of cement and anhydrous gypsum.

The EP-A 799 807 again describes the use of comb polymers based on monoethylenically unsaturated Monocarboxylic acids and alkylpolyalkylene glycol mono (meth) acrylic esters, the latter being characterized by a transesterification process available are, as dispersants for Cement.

The US 5,728,207 and US 5,840,114 describe the use of comb polymers obtained by polymer modification of polymers having cyclic anhydride groups with alkylpolyalkylene ether amines as additives to cementitious formulations.

Out WO 98/28353 discloses comb polymers having a carbon backbone, the alkylpolyalkylene ether groups and carboxylate groups. The Comb polymers can both by modification of polymers containing carboxylate groups with polyalkylene ethers as well as by copolymerization suitable, Alkylpolyalkylenether groups containing monomers with ethylenic unsaturated carboxylic acids getting produced.

WO 01/74736 in turn describes comb polymers of poly-C ₂ -C ₄ -alkylene glycol (meth) acrylic esters with (meth) acrylic acid, wherein the preparation of the poly-C ₂ -C ₄ -alkylene glycol (meth) acrylates by Reaction of Alkylpolyalkylenglykolen with (meth) acrylic anhydrides in the presence of amines takes place.

The earlier patent application PCT / EP009466 describes comb polymers similar to those of WO 01/74736, wherein the poly-C ₂ -C ₄ -alkylene glycol (meth) acrylates used for the preparation of the polymers by reaction of Alkylpolyalkylenglykolen with (meth) acrylic anhydrides in the presence of a reaction medium insoluble base are available.

The US 3,651,029 describes the use of oil-soluble comb polymers with polyalkylene ether side chains bearing at their ends a morpholin-4-yl radical as additives for lubricants.

The EP-A 704 504 describes homo- and copolymers of esters ethylenically unsaturated carboxylic acids with polyalkylene etherols having a nitrogen heterocycle at one end wear. The polymers described there are used as temperature-dependent thickeners used in ink-jet inks.

The dispersing effect of the comb polymers of the prior art is common insufficient, so that their liquefying Effect in preparations based on mineral binders such as Gypsum or cement is not satisfactory. Own investigations of the Inventors of the present application have also shown that the Of the prior art comb polymers often still bigger amount contain unreacted polyalkylene glycol monomethyl ethers, they themselves are not liquefying Have effect, so that larger quantities comb polymer needed to achieve the desired effect, which on the one hand an additional one Cost factor and on the other hand with regard to this increased Foaming is also undesirable.

Of the The present invention is therefore based on the object, additives for preparations based on mineral binders that provide a good liquefying Show effect in such preparations. The additives should They can also be made in a way that they are low or contain no amounts of by-products.

It was surprisingly found that this problem is solved by comb polymers with a carbon backbone, the at the polymer backbone Polyether groups of the formula A defined below and functional Groups B, which at pH> 12 in the form of anionic groups.

Accordingly, the present invention relates to the use of comb polymers having a carbon backbone, the polyether groups of the formula A. * -U- (C (O)) _k -X- (Alk-O) _n -YZ A wherein
* indicates the binding site to the carbon backbone of the comb polymer,
U is a chemical bond or an alkylene group having 1 to 8 carbon atoms,
X represents oxygen or a group NR,
k is 0 or 1,
n is an integer whose mean value, based on the comb polymer, is in the range from 5 to 300,
Alk is C ₂ -C ₄ -alkylene, where Alk within the group (Alk-O) _{n may be} identical or different,
Y is a linear or branched alkylene group having 2 to 8 C atoms, which may carry a phenyl ring,
Z is a nitrogen-bonded 5- to 10-membered nitrogen heterocycle which, as ring members, in addition to the nitrogen atom and in addition to carbon atoms, 1, 2 or 3 may have additional heteroatoms selected from oxygen, nitrogen and sulfur, wherein the nitrogen ring members a group R 'and wherein 1 or 2 carbon ring members may be present as carbonyl group,
R is hydrogen, C ₁ -C ₄ alkyl or benzyl, and
R 'is hydrogen, C ₁ -C ₄ alkyl or benzyl;
and functional groups B which are present in the form of anionic groups at pH> 12,
and their salts as additives in preparations containing a mineral binder. The invention also relates to preparations of mineral binders containing such a comb polymer, in particular ready-to-use preparations and the articles produced therefrom.

Such comb polymers are novel when the average of n, based on the comb polymer, is in the range of 10 to 300 and on average 90 mole% of the units Alk-O in the group (Alk-O) _n for CH ₂ -CH ₂ -O stand.

Accordingly, the present invention also relates to comb polymers having a carbon backbone, the polyether groups of the general formula A and functional groups B, which are present at pH> 12 in the form of anionic groups, wherein in formula A the variables *, U, X, k Alk, Y, Z, R and R 'have the abovementioned meanings and n is an integer whose mean value based on the comb polymer is in the range from 10 to 300 and in which at least 90 mol% of the units Alk -O in the group (Alk-O) _{n is} CH ₂ -CH ₂ -O.

According to the invention the comb polymers used to additize preparations, containing mineral binders. With the invention for use coming comb polymers leaves to achieve a liquefaction of the preparations in a particularly effective manner, d. H. the amount needed to set the desired processing viscosity on mixing water, based on the mineral binder, can in comparison to non-additive preparations or in comparison to additive preparations of mineral binders, in which the additives have a lower liquefying effect, reduced or, alternatively, to adjust a certain viscosity of the preparation required application rate of comb polymer is lower compared to the comb polymers of State of the art.

Mineral Binders in the context of the present invention are inorganic, usually mineral substances that when mixed with water hardened to a solid. This is different under substances that harden in the air (non-hydraulic binders or air binder), z. Gypsum, corrosive cement, magnesia binder and white lime, and hydraulic binders such as lime and especially cement, including latent hydraulic binders, such as blast furnace slags. This here The term "gypsum" used includes both anhydrite as well as calcium sulfate hemihydrate.

The comb polymers according to the invention are particularly suitable for the addition of preparations hydraulic Binders and especially for the additive cementitious Preparations, but also for the addition of preparations latenthydraulischer Binder.

The comb polymers according to the invention are also suitable for the addition of preparations non-hydraulic Binders, in particular for the addition of gypsum and gypsum-containing Preparations such as model stucco or plaster, plaster, gypsum plaster.

The comb polymers according to the invention are also particularly suitable for the addition of preparations, as a mineral binder a mixture of a hydraulic and a non-hydraulic binder, e.g. B. a mixture of Plaster and cement, included.

The Comb polymers can both for the additivation of preparations, which are essentially consist of the mineral binder used. she However, they are also particularly suitable for the addition of binders, d. H. Preparations containing as main ingredient additives which tied by the mineral binder, for example for the addition of concrete and mortar.

at the invention additivierten Preparations of the mineral binder may be storage forms of the mineral binder, to form bearings of the binding material, or to be ready-to-use preparations, i. to preparations, which, in contrast to the forms of storage already for the binding of the Binder or building material required amount of water (mixing water) contain.

Here and below, C ₂ -C ₄ -alkylene is a linear or branched alkanediyl group which has 2 to 4 C atoms, in particular a 1,2-ethanediyl group which can carry one or two methyl groups or one ethyl group, ie for 1,2-ethanediyl, 1,2-propanediyl, 1,2-butanediyl, 1,1-dimethylethane-1,2-diyl or 1,2-dimethylethane-1,2-diyl.

C ₁ -C ₈ -alkylene represents a linear or branched alkanediyl group having 1 to 8 and in particular 1 to 4 carbon atoms, for. For example, CH ₂ , 1,1-ethanediyl, 1,2-ethanediyl, 1,1-propanediyl, 1,3-propanediyl, 2,2-propanediyl, 1,2-propanediyl, 1,1-butanediyl, 1, 2-butanediyl, 1,3-butanediyl, 1,4-butanediyl, 2,2-butanediyl, 1,1-dimethylethane-1,2-diyl or 1,2-dimethylethane-1,2-diyl.

C ₁ -C ₄ alkyl represents a linear or branched alkyl group having 1 to 4 C atoms, for. For example, methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-butyl, 2-methylpropan-1-yl or tert-butyl. C ₁ -C ₁₀ alkyl stands for a linear or branched alkyl group having 1 to 10 C atoms, e.g. B. for C ₁ -C ₄ alkyl, as mentioned above, and for pentyl, hexyl, 1-methylpentyl, 2-methylpentyl, heptyl, octyl, 1-methylheptyl, 2-methylheptyl, 2,4,4-trimethylpentane-2 -yl, 2-ethylhexyl, 1-ethylhexyl, nonyl, isononyl, decyl, 1-methylnonyl, 2-propylheptyl and the like.

C ₁ -C ₄ -alkoxy represents a linear or branched alkyl group which is bonded via an oxygen atom and which has 1 to 4 carbon atoms, eg. For example, methoxy, ethoxy, n-propyloxy, isopropyloxy, n-butyloxy, 2-butyloxy, 2-methylpropan-1-ylxoy or tert-butoxy. C ₁ -C ₁₀ alkoxy represents a linear or branched alkyl group which is bonded via an oxygen atom and which has 1 to 10 C atoms, eg. B. for C ₁ -C ₄ alkoxy, as mentioned above, and for pentyloxy, hexyloxy, 1-methylpentyloxy, 2-Methylpentylxoy, heptyloxy, octyloxy, 1-methylheptyloxy, 2-Methylheptylxoy, 2,4,4-trimethylpentane-2 -yloxy, 2-ethylhexyloxy, 1-ethylhexyloxy, nonyloxy, isononyloxy, decyloxy, 1-methylnonyloxy, 2-propylheptyloxy and the like.

With regard to the use according to the invention, it has proven advantageous if the average number of repeat units Alk-O in the groups (Alk-O) _n , ie the mean value of n in formula A, based on the comb polymer, is at least 10, in particular is at least 20 and especially at least 50 and does not exceed a value of 250, in particular 200 and especially 150. The value is preferably in the range from 10 to 250, in particular in the range from 20 to 200 and especially in the range from 50 to 150. The mean value of n or the average number of repeat units Alk-O is the number average on the comb polymer.

In the group (Alk-O) _n , the alkylene moieties of the individual repeat units Alk-O may be the same or different. Alk-O particularly preferably represents 1,2-ethanediyl or mixtures of 1,2-ethanediyl with 1,2-propanediyl. If the groups (Alk-O) have _n different units Alk-O, they may be arranged randomly or in blocks, wherein a block-wise arrangement is preferred. In particular, that group Alk-O attached to X is a group of the formula CH ₂ CH ₂ O.

Furthermore, it has proved to be advantageous if at least 50 mol%, in particular at least 80 mol%, particularly preferably 90 mol% and in particular all groups Alk-O are CH ₂ -CH ₂ -O. These% data are the number average, based on the total amount of comb polymer.

If the group (Alk-O) _{n has} different repeat units Alk-O, it has proved to be advantageous if on average at least 50 mol%, z. B. 50 to 99 mol%, in particular at least 80 mol%, z. B. 80 to 99 mol%, and especially at least 90 mol%, z. B. 90 to 98 mol% of the groups Alk-O are CH ₂ -CH ₂ -O. Of these, preference is given to those mixtures in which the remaining repeat units Alk-O are CH (CH ₃ ) -CH ₂ -O.

The Group Z in formula A is preferably a 5- or 6-membered Nitrogen heterocycle, which in addition to the nitrogen atom bound to Y. and the carbon ring members among O, S, N, of a group NR selected Ring member and / or a carbonyl group as a ring member. In the group NR has the meanings given above and stands in particular for hydrogen or methyl. Of these, preference is given to those heterocycles which have a ring member selected from O, N or a group NR and / or a carbonyl group have as a ring member. Examples of preferred radicals Z are pyrrolidon-1-yl, Morpholin-4-yl, piperazin-1-yl, piperidone-1-yl, morpholin-2-one-4-yl, Morpholin-3-one-4-yl, piperazin-1-yl, 4-methylpiperazin-1-yl, imidazolin-2-one-1-yl, 3-methylimidazolin-2-one-1-yl and imidazol-1-yl. These include in particular morpholin-1-yl and pyrrolidone-1-yl are preferred.

Furthermore, it has proved to be advantageous if Y in formula A is C ₂ -C ₄ -alkylene and in particular 1,2-ethanediyl or 1,3-propanediyl.

U is preferably a chemical bond, CH ₂ or CH (CH ₃ ). In a particularly preferred embodiment, U is a chemical bond.

Especially k stands for 1.

In Formula A is preferably X for O or NH and in particular for O.

Especially In formula A, the variables U, k, X, Y and Z and the variable n together have the meanings mentioned as preferred.

The groups B present in the comb polymers used according to the invention are typically present at pH values above 12 in the form of anionic groups, ie in deprotonated form. Examples of such groups are carboxylate (COOH or COO ^- ), sulfonate (SO ₃ H or SO ₃ ^- ), phosphonate (PO ₃ H ₂ or PO ₃ H ^- or PO ₃ ^2- ). Preferably at least 50 mol%, in particular at least 80 mol% of the groups B are carboxylate groups.

In a preferred embodiment of the invention, group B is essentially (i.e. at least 95 mol%, especially at least 99 mol%) or exclusively around Carboxylate groups. In another embodiment of the invention the comb polymers at least two different functional groups B on, in this embodiment preferably 50 to 99 mol%, in particular 80 to 99 mol% of the functional Groups B carboxylate groups and the remaining 1 to 50 mol%, in particular 1 to 20 mol%, are sulfonate groups.

The functional groups B can be bonded directly or via a spacer to the carbon backbone of the polymer chain. Typical spacers are C ₁ -C ₄ alkanediyl, phenylene and groups of the formula * -C (O) -X-Alk'-, in which X 'is O, NH or N (C ₁ -C ₄ -alkyl), Alk' is C ₂ -C ₄ -alkylene, in particular 1,2-ethanediyl, 1,3-propanediyl, 1,2-propanediyl or 1-methyl-1,2-propanediyl and is the binding site of the spacer to the polymer backbone. In a preferred embodiment of the invention, the group B is bonded directly, ie via a single bond, to the carbon backbone of the comb polymer.

Furthermore, in addition to the abovementioned groups of the formula A and the functional groups B, the comb polymer can also be groups of the formula C * -U '- (C (O)) _p -X "- (Alk" -O) _q -R ^a C wherein
U 'has the meanings given for U, p is 0 or 1, X''has the meanings given for X, Alk''has the meanings given above for alk, q is an integer whose mean value, based on the Comb polymer in the range of 2 to 300, in particular in the range of 10 to 250, more preferably in the range of 20 to 200 and especially in the range of 50 to 150 (number average) and R ^{a is} selected from hydrogen, C ₁ -C ₁₀ - Alkyl, C ₁ -C ₁₀ alkylcarbonyl, benzyl or benzoyl. In formula C, p is in particular 1. U 'is in particular a chemical bond. X "is in particular oxygen. R ^a is in particular C ₁ -C ₄ -alkyl and especially methyl. With regard to the preferred meanings of Alk '', what has been said above for Alk applies analogously.

In principle, the polyether groups A but also the polyether groups C within the comb polymer with respect to the number of repeating units n or q in the groups (Alk-O) _n or (Alk '' - O) _{q may be the} same or different, taking into account in that the groups A and C or the groups (Alk-O) _n or (Alk '' - O) _{q have} a molecular weight distribution and accordingly represent n and q average values (number average) of these molecular weight distributions. The term "equal" therefore means that the molecular weight distribution of the groups A and C each have a maximum. Accordingly, the term "different" means that the molecular weight distribution of the groups A and C corresponds to several superimposed distributions and accordingly have several maxima. Comb polymers in which the molecular weight distributions of the groups A or, when present, the molecular weight distributions of the groups A are different from those of the groups C are preferred. In particular, those comb polymers are preferred where the respective maximum number average molecular weight deviates from one another by at least 130 daltons and in particular at least 440 daltons. Accordingly, comb polymers are preferred which contain at least two, e.g. B. 2, 3, 4, 5 or 6 types of different groups A have (hereinafter groups A1 and A2 or A1, A2 ... Ai; i an integer, eg 3, 4, 5 or 6) in which the respective average values n (A1) and n (A2) or n (Ai) differ by a value of at least 3 and in particular by at least 10. Accordingly, comb polymers having groups of the formula A and of the formula C are preferred in which the mean values of n and q differ by a value of at least 3 and in particular by at least 10.

In the comb polymers used according to the invention, the polyether groups of the formula A and the functional groups B are typically in a molar ratio A: B in the range from 2: 1 to 1:20, frequently in the range from 1.5: 1 to 1:15, especially in the range of 1: 1 to 1:10 and especially in the field from 1: 1.1 to 1: 8 before (averaged over the total amount of comb polymers). If the comb polymer has polyether groups of the formula C, the molar ratio of polyether groups of the formula A and C to the functional groups B, ie the molar ratio (A + C): B is typically in the range from 2: 1 to 1:20, often in the range from 1.5: 1 to 1:15, in particular in the range from 1: 1 to 1:10 and especially in the range from 1: 1.1 to 1: 1 (averaged over the total amount of comb polymers)

In addition to the abovementioned groups of the formula A, the functional groups B and the optionally present groups C, the comb polymer may to a lesser extent also carry functional groups C 'on the carbon backbone. These include in particular C ₁ -C ₈ -alkoxycarbonyl groups in which the alkoxy radical may carry one or more hydroxyl groups, nitrile groups and groups of the formula Z as defined above.

Of the Proportion of functional groups C 'is based on the total amount of functional groups A, B, optionally C and C 'preferably 30 mol%, in particular 20 mol% does not exceed and is, if present, typically in the range of 1 to 30 mol% and in particular in the range of 2 to 20 mol%. In a preferred embodiment the comb polymer has no or less than 2 mol%, in particular less than 1 mol% of functional groups C '.

In a preferred embodiment the comb polymer has 5 to 80 mol%, in particular 10 to 60 mol%, in each case based on the total amount of the functional groups A, B, C and optionally C 'groups of the formula C on. In this embodiment is the molar ratio side chains A to groups C, d. H. the molar ratio A: C preferably in the range from 1:10 to 20: 1, in particular in the range from 1: 2 to 10: 1. In another preferred embodiment of the invention, the comb polymer has no or less than 5 mol%, in particular less than 1 mol%, Groups of formula C ', in each case based on the total amount of the groups A, B, C and C '.

In addition, the comb polymer may also have hydrocarbon radicals on the carbon backbone, e.g. B. C ₁ -C ₄ alkyl groups or phenyl groups. In a preferred embodiment of the invention, the carbon backbone has C ₁ -C ₄ -alkyl groups, in particular methyl groups, on at least every 4 C atom of the polymer chain.

Farther it has proved to be advantageous if on average (number average) at least every 4th carbon atom of the polymer backbone, and especially at least every 3rd carbon atom is a group of the formula A or, where appropriate, C or a functional group B carries. Furthermore, it has as proved advantageous when on average (number average) between two by A, B or optionally C-substituted carbon atoms of the polymer backbone at least one carbon atom is arranged, not by a Group A, B or optionally C is substituted.

The number-average molecular weights (M _N ) of the comb polymers are generally in the range from 1000 to 200,000. With regard to the use of the comb polymers, those with a number-average molecular weight of 5,000 to 100,000 are preferred. The number average molecular weight M _N can be determined in a conventional manner by gel permeation chromatography, as illustrated in the examples. The K values of the copolymers obtainable according to the invention, determined by the method indicated below, are generally in the range from 10 to 100, preferably in the range from 15 to 80 and in particular in the range from 20 to 60.

The comb polymers can be used in the form of the free acid or in the form of their salts, it being possible for the groups B to be partially or completely neutralized in the salt form. If the comb polymers are used in the form of the salts, they have cations as counterions for reasons of electroneutrality. Suitable cations are alkali metal cations such as Na ⁺ and K ⁺ , alkaline earth metal cations such as Mg ⁺⁺ and Ca ⁺⁺ , and ammonium ions such as NH ₄ ⁺ , [NR ^b R ^c R ^d R ^e ] ⁺ , where R ^{b is} C ₁ -C ₄ Alkyl or hydroxy-C ₂ -C ₄ alkyl and the radicals R ^c , R ^d and R ^{e are} independently selected from hydrogen, C ₁ -C ₄ alkyl and hydroxy-C ₂ -C ₄ alkyl. Preferred counterions are the alkali metal cations, especially Na ⁺ and K ⁺ .

The Preparation of the comb polymers of the invention can in analogy to known processes for the preparation of such Comb polymers take place, for. B. in analogy to the methods as they in the cited prior art are described as well in analogy to those in WO 01/40337, WO 01/40338, WO 01/72853 or WO 02/50160 described in the disclosure of which hereby Reference is made.

• i) Copolymerisation ethylenisch ungesättigter Monomere M, umfassend a) neutrale monoethylenisch ungesättigte Monomere M1, die eine oder zwei Gruppen der Formel A aufweisen, und b) monoethylenisch ungesättigte Monomere M2, die eine oder zwei funktionelle Gruppe B aufweisen,
• ii) Homo- oder Copolymerisation ethylenisch ungesättigter Monomere M, umfassend a) monoethylenisch ungesättigte Monomere M3, die eine Gruppe der Formel A und eine funktionelle Gruppe B aufweisen, und gegebenenfalls b) monoethylenisch ungesättigte Monomere M2, die eine oder zwei funktionelle Gruppe B aufweisen, sowie
• iii) polymeranaloge Umsetzung von Homo- oder Copolymeren mit einem Kohlenstoffrückgrat, die freie Carboxylgruppen oder esterbildende Derivate von Carboxylgruppen aufweisen, mit Alkoholen der Formel HO-(Alk-O)_n-Y-Z oder Aminen der Formel HNR-(Alk-O)_n-Y-Z worin n, Alk, R, Y und Z die zuvor genannten Bedeutungen aufweisen.

Suitable production processes are in particular:

• i) copolymerization of ethylenically unsaturated monomers M, comprising a) neutral monoethylenically unsaturated monomers M1 which have one or two groups of the formula A, and b) monoethylenically unsaturated monomers M2 which have one or two functional groups B,
• ii) Homo- or copolymerization of ethylenically unsaturated monomers M comprising a) monoethylenically unsaturated monomers M3 which have a group of the formula A and a functional group B, and optionally b) monoethylenically unsaturated monomers M2 which have one or two functional groups B, such as
• iii) polymer-analogous reaction of homopolymers or copolymers having a carbon backbone which have free carboxyl groups or ester-forming derivatives of carboxyl groups, with alcohols of the formula HO- (Alk-O) _n -YZ or amines of the formula HNR- (Alk-O) _n - YZ in which n, Alk, R, Y and Z have the abovementioned meanings.

The three production processes i), ii) and iii) all lead to comb polymers according to the invention, the structure of the comb polymers obtainable thereby naturally being dependent on the particular production method chosen and the amount and type of starting materials used in a manner known per se. Thus, for example, in the case of the comb polymers obtainable by preparation methods i) and ii), the type and amount of side chains A or functional groups B depends on the type and relative amount of monomers M1 and M2 or M1 used and, if appropriate, M3 in in a known manner. The molecular weight of the comb polymers in turn can be in the production methods i) and ii) by the reaction conditions selected in the polymerization, for. B. by the initiator used, optionally used regulators, the temperature, the reaction medium, concentration of monomers, etc. in a conventional manner. In the case of the comb polymers obtainable by the preparation method iii), the structure and the molecular weight are naturally determined by the homo- or copolymers used and by the alcohols used for the modification HO- (alk-O) _n -YZ or amines of the formula HNR- (alkoxy) O) _n -YZ largely determined.

According to the invention preferred are available by the method i) Comb polymers, thus a particularly preferred subject of the Form invention.

in the Production process i) determine the type and amount of monomers M the type and number of side chains of formula A.

Preferred monomers M1 are those in which k in formula A is 1. Preferred monomers M1 are therefore selected from the esters of monoethylenically unsaturated C ₃ -C ₈ -monocarboxylic acids and diesters of monoethylenically unsaturated C ₄ -C ₈ -dicarboxylic acids with alcohols of the formula HO- (Alk-O) _n -YZ, where n, Alk, Y and Z have the abovementioned meanings, and the amides of monoethylenically unsaturated C ₃ -C ₈ -monocarboxylic acids with amines of the formula NHR- (Alk-O) _n -YZ, where n, Alk, R, Y and Z have the abovementioned meanings ,

Preferred esters of monoethylenically unsaturated C ₃ -C ₈ monocarboxylic acids are the esters of acrylic acid and of methacrylic acid.

Examples of diesters of monoethylenically unsaturated C ₄ -C ₈ -dicarboxylic acids are the esters of fumaric acid, itaconic acid and maleic acid.

Preferred amides of monoethylenically unsaturated C ₃ -C ₈ monocarboxylic acids are the amides of acrylic acid and of methacrylic acid.

Further suitable monomers M1 are vinyl, allyl and methallyl ethers of alcohols of the formula HO- (Alk-O) _n -YZ, in which n, Alk, Y and Z have the abovementioned meanings.

Preferably, the monomers M1 comprise at least 80 mol%, in particular at least 90 mol%, based on the total amount of the monomers M1, esters of monoethylenically unsaturated C ₃ -C ₈ monocarboxylic acids, in particular esters of acrylic acid and methacrylic acid. In particular, the monomers M1 are selected from the aforementioned esters of monoethylenically unsaturated C ₃ -C ₈ monocarboxylic acids, and especially selected from the esters of acrylic acid and methacrylic acid.

The monomers M2 include:
M2a monoethylenically unsaturated mono- and dicarboxylic acids having 3 or 4 to 8 carbon atoms, such as acrylic acid, Methacrylic acid, crotonic acid, isocrotonic acid, maleic acid, fumaric acid and itaconic acid.
M2b monoethylenically unsaturated sulfonic acids having preferably 2 to 10 carbon atoms and salts thereof, in particular their alkali metal salts such as vinylsulfonic acid, allylsulfonic acid, methallylsulfonic acid, styrenesulfonic acid, 2-acryloxyethanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, and
M2b monoethylenically unsaturated phosphonic acids having preferably 2 to 10 C atoms, such as vinylphosphonic acid, allylphosphonic acid, 2-acryloxyethanephosphonic acid, 2-acrylamido-2-methylpropanephosphonic acid,
M2d monoesters of monoethylenically unsaturated dicarboxylic acids having 4 to 8 C atoms, in particular half esters of maleic acid, fumaric acid and itaconic acid with C ₁ -C ₁₀ -alkanols, in particular with C ₁ -C ₄ -alkanols, eg. B. the monomethyl, monoethyl or monobutyl esters of these acids and the monoesters of these acids with alcohols of the formula HO (Alk '' - O) _q -R ^a , wherein q, Alk '' and R ^{a have} the meanings given above,
and the salts of these monomers, especially their alkali metal salts.

preferred Monomers M2 comprise at least 50 mol%, especially at least 70 mol%, based on the total amount of monomers M2, monoethylenic unsaturated Mono- and dicarboxylic acids with 3 or 4 to 8 carbon atoms, and among these, particularly preferably acrylic acid and Methacrylic acid. In a preferred embodiment the monomers M2 are selected under monoethylenically unsaturated Mono- and dicarboxylic acids with 3 or 4 to 8 C atoms, in particular with acrylic acid and Methacrylic acid. In another embodiment of the invention, the monomers M2 comprise 50 to 99 mol%, in particular 70 to 95 mol%, based on the total amount of monomers M2, of monoethylenic unsaturated Mono- and dicarboxylic acids with 3 or 4 to 8 carbon atoms, and among these, particularly preferably acrylic acid and Methacrylic acid, as well 1 to 50 mol%, in particular 5 to 35 mol%, based on the total amount of the monomers M2, monoethylenically unsaturated sulfonic acids with preferably 2 to 10 carbon atoms.

Monomers M3 include, in particular, monoesters of monoethylenically unsaturated C ₄ -C ₈ -dicarboxylic acids with alcohols of the formula HO- (Alk-O) _n -YZ, in which n, Alk, Y and Z have the abovementioned meanings, especially the half esters of maleic acid , fumaric acid and itaconic acid.

Besides can the monomers M comprise further monomers M4 and M5.

Monomeric M4 are monoethylenically unsaturated monomers which have one or two groups of the formula C and, if appropriate, a functional group B. These include vinyl, allyl and methallyl ethers of alcohols of the formula HO (Alk "- O) _q -R ^a , in which q, Alk" and R ^{a have} the meanings given above, furthermore the esters of these alcohols of monoethylenically unsaturated mono- C ₃ -C ₈ -carboxylic acids and the diesters and half of these alcohols with monoethylenically unsaturated di-C ₄ -C ₈ -carboxylic acids. Preferred monomers M4 are esters of monoethylenically unsaturated mono-C ₃ -C ₈ -carboxylic acids, in particular of acrylic acid and of methacrylic acid, with alcohols of the formula HO (Alk "- O) _q -R ^a , in which q, Alk" and R ^a have the abovementioned meanings, and diesters of monoethylenically unsaturated di-C ₄ -C ₈ -carboxylic acids, in particular maleic acid, fumaric acid, citraconic acid and itaconic acid, with alcohols of the formula HO (Alk "-O) _q -R ^a , Particularly preferred monomers M4 are the esters of monoethylenically unsaturated mono-C ₃ -C ₈ -carboxylic acids, in particular of acrylic acid and methacrylic acid.

Preferably do not make the monomers M4 more than 80 mol%, especially not more than 60 mol%, based on the total amount of the monomers M, from. In a preferred embodiment of the invention the proportion of the monomers M4 5 to 80 mol%, in particular 10 to 60 mol%, based on the total amount of monomers M in the preparation process i) or ii). In another embodiment of the invention, their share on the monomers M less than 5 mol%, in particular less than 1 mol%. In terms of the molar ratio from monomers M1 to M4 or from monomers M3 to M4, the above applies for the molar ratio of the functional groups A: C in a similar way.

The monomers M5 include the monomers M5a, M5b, MSc, M5d and M5e:
M5a C ₁ -C ₂₀ -alkyl esters and C ₅ -C ₁₀ -cycloalkyl esters of monoethylenically unsaturated mono-C ₃ -C ₈ -carboxylic acids, in particular of acrylic acid and of methacrylic acid, with C ₁ -C ₁₀ -alkanols or C ₃ -C ₁₀ - Cycloalkanols such as methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate and the corresponding methacrylic acid esters, and corresponding di-C ₁ -C ₁₀ - Alkyl esters and di-C ₅ -C ₁₀ -cycloalkyl esters of monoethylenically unsaturated di-C ₄ -C ₈ -carboxylic acids;
M5b hydroxy-C ₂ -C ₁₀ -alkyl esters of monoethylenically unsaturated mono- and di-C ₃ -C ₈ -carboxylic acids, in particular of acrylic acid and of methacrylic acid, such as 2-hydroxyethyl acrylate, 3-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 2-hydroxyethylmethane acrylate, 3-hydroxypropyl methacrylate and 4-hydroxybutyl methacrylate,
M5c monoethylenically unsaturated nitriles such as acrylonitrile,
M5d vinylaromatic monomers such as styrene and vinyltoluenes,
M5e olefins having preferably 2 to 12 C atoms, such as ethylene, propene, 1-butene, isobutene, 1-hexene, diisobutene, 1-octene, 1-decene, 1-dodecene, etc.

preferred Monomers M5 are the monomers M5b.

Preferably the monomers M5 do not make up more than 30 mol%, especially not more than 20 mol%, based on the total amount of the monomers M, from. If desired, is their proportion is usually 1 to 30 mol%, especially 5 to 20 mol% of Monomers M in preparation process i) or ii). In particular their proportion of the monomers M less than 5 mol%, in particular less as 1 mol%.

at the method i) gives the molar ratio of side chains A to functional groups B, optionally C and C 'usually directly from the molar ratio the monomers M1 to the monomers M2 or from the molar ratio of Monomers M1: M2: M4: M5. Accordingly, the molar ratio M1: M2 or (M1 + M4): M2 in the case of monovalent acids usually in the range from 2: 1 to 1:20, especially in the range of 1: 1 to 1:10 us specifically in the range of 1: 1.1 to 1: 8. If the monomers M in the production process i) monomers M2 with more than one acid group or monomers M3 include the molar ratio the monomers in a corresponding manner.

Accordingly is the amount of monomers M1 in the preparation process i) typically 5 to 65 mol%, especially 10 to 50 mol% and the amount of the monomers M2 35 to 95 mol%, in particular 50 to 90 mol%, wherein the proportion any further monomers M3 or M5, up to 30 mol%, in particular bis may be up to 20 mol% and the proportion of monomers M4 up to 80 mol%, in particular up to 60 mol%, z. B. 5 to 80 mol%, in particular 10 to 60 mol%, in each case based on the total moles of monomers M, which may be, of course, the molar numbers of all monomers Add M to 100 mol%, unless stated otherwise.

at the process ii) gives the molar ratio of side chains A to functional groups B in analogous to the method i) the molar ratio the monomers M3 to the optionally used monomers M2 or M1 or M4. The same applies to the relationship between the molar ratio from side chains A to side chains C or to functional groups B.

Accordingly is the amount of monomers M3 in the production process ii) typically 40 to 100 mol%, in particular 50 to 95 mol% and the amount of the monomers M2 0 to 60 mol%, in particular 5 to 50 mol%, wherein the number of moles any further monomers M2 or M5, up to 30 mol%, in particular can be up to 20 mol% and the proportion of monomers M4 up to 80 mol%, in particular up to 60 mol%, z. B. 5 to 80 mol%, in particular 10 to 60 mol%, in each case based on the total moles of monomers M, which may be, of course, the molar numbers of all monomers Add M to 100 mol%, unless stated otherwise.

In addition, can it to increase the molecular weight of the polymers be useful, the polymerization the monomers M in the presence of small amounts of multi-ethylenic unsaturated Monomers with z. B. 2, 3 or 4 polymerizable double bonds perform (Crosslinker). examples for this are Diesters and triesters of ethylenically unsaturated carboxylic acids, in particular the bis- and tris-acrylates of diols or polyols of 3 or more OH groups, eg. B. the bisacrylates and the bismethacrylates of ethylene glycol, Diethylene glycol, triethylene glycol, neopentyl glycol or polyethylene glycols. Such crosslinkers are, if desired, in an amount of in usually 0.01 to 5 wt .-% based on the total amount of the polymerized Monomers M used. Preferably less than 0.01% by weight and in particular no Vernetzermonomere used.

The Polymerization of the monomers M is usually carried out in the presence of Radical forming compounds, so-called initiators. such Connections usually become in amounts up to 30 wt .-%, preferably 0.05 to 15 wt .-%, in particular 0.2 to 8 wt .-%, based on the monomers to be polymerized used. In multi-constituent initiators (Initiator systems, for example, in the case of redox initiator systems) relate the above weights are based on the sum of the components.

Suitable initiators are, for example, organic peroxides and hydroperoxides, furthermore peroxodisulfates, percarbonates, peroxide esters, hydrogen peroxide and azo compounds. Examples of initiators are hydrogen peroxide, dicyclohexyl peroxydicarbonate, diacetyl peroxide, di-tert-butyl peroxide, diamyl peroxide, dioc tanoyl peroxide, didecanoyl peroxide, dilauroyl peroxide, dibenzoyl peroxide, bis (o-toluyl) peroxide, succinyl peroxide, methyl ethyl ketone peroxide, di-tert-butyl hydroperoxide, acetylacetone peroxide, butyl peracetate, tert-butyl permalate, tert-butyl perisobutyrate, tert-butyl perpivalate, tert-butyl peroctoate , tert-Butylperneodecanoat, tert-butyl perbenzoate, tert-butyl hydroperoxide, cumene hydroperoxide, tert-Butylperneodecanoat, tert-amyl perpivalate, tert-butyl perpivalate, tert-butyl perbenzoate, tert-butyl peroxy-2-ethylhexanoate and Diisopropylperoxidicarbamat ; furthermore, lithium, sodium, potassium and ammonium peroxodisulfate, azo initiators 2,2'-azobisisobutyronitrile, 2,2'-azobis (2-methylbutyronitrile), 2,2'-azobis [2-methyl-N - (- 2 -hydroxyethyl) propionamide, 1,1'-azobis (1-cyclohexanecarbonitrile), 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (N, N'-dimethyleneisobutyroamidine) dihydrochloride, and 2, 2'-azobis (2-amidinopropane) dihydrochloride. as well as the redox initiator systems explained below.

Redox initiator systems contain at least one peroxide-containing compound in combination with a redox coinitiator, e.g. B. a reducing sulfur compound, z. Bisulfites, sulfites, thiosulfates, dithionites and tetrathionates of alkali metals or of ammonium compounds. So you can do combinations of peroxodisulfates with alkali metal or ammonium hydrogen sulfites use, for. For example, ammonium peroxodisulfate and ammonium disulfite. The Amount of the peroxide-containing compound to the redox coinitiator is 30: 1 to 0.05: 1.

The Initiators can used alone or mixed with each other, for. B. mixtures Hydrogen peroxide and sodium peroxodisulfate.

The Initiators can both water soluble as well as in water or only slightly soluble. For the polymerization in watery Medium are preferably water-soluble Initiators used, d. H. Initiators used in the polymerization used concentration in aqueous Polymerization medium soluble are. Which includes Peroxodisulfates, azo initiators with ionic groups, organic Hydroperoxides containing up to 6 C atoms, acetone hydroperoxide, methyl ethyl ketone hydroperoxide and hydrogen peroxide, as well as the aforementioned redox initiators. In a particularly preferred embodiment of the polymerization process i) or ii) the initiator used comprises at least one peroxodisulfate, z. For example, sodium peroxodisulfate.

In Combination with the initiators or the redox initiator systems can additionally transition metal catalysts be used, for. Salts of iron, cobalt, nickel, copper, Vanadium and manganese. Suitable salts are, for. B. ferrous sulfate, Cobalt (II) chloride, nickel (II) sulfate, or copper (I) chloride. Based On the monomers, the reducing transition metal salt in a Concentration of 0.1 ppm to 1000 ppm used. So you can do combinations of hydrogen peroxide with iron (II) salts, such as 0.5 to 30% hydrogen peroxide and 0.1 to 500 ppm Mohr's salt.

Also in the polymerization of the monomers M in organic solvents can in combination with the abovementioned initiators redox coinitiators and / or transition metal catalysts be used, z. B. benzoin, dimethylaniline, ascorbic acid and in organic solvents soluble Complexes of heavy metals such as copper, cobalt, iron, manganese, Nickel and chrome. The usual used amounts of redox coinitiators or transition metal catalysts be about 0.1 to 1000 ppm, based on the amounts used at monomers.

In order to control the average molecular weight of the comb polymers obtainable according to the invention, it is often expedient to carry out the polymerization of the monomers M in the presence of regulators. Conventional regulators may be used for this purpose, in particular compounds containing organic SH groups, in particular water-soluble compounds containing SH groups, such as 2-mercaptoethanol, 2-mercaptopropanol, 3-mercaptopropionic acid, cysteine, N-acetylcysteine, furthermore phosphorus (III) or phosphorus ( I) compounds such as alkali metal or Erdalkalimetallhy pophosphite, z. As sodium hypophosphite, and hydrogen sulfites such as sodium hydrogen sulfite. The polymerization regulators are generally used in amounts of from 0.05 to 10% by weight, in particular from 0.1 to 2% by weight, based on the monomers M. Preferred regulators are the abovementioned SH-group-carrying compounds, in particular water-soluble compounds bearing SH groups, such as 2-mercaptoethanol, 2-mercaptopropanol, 3-mercaptopropionic acid, cysteine and N-acetylcysteine. In these compounds, it has proven particularly useful to use these in an amount of 0.05 to 2 wt .-%, in particular 0.1 to 1 wt .-%, based on the monomers. The aforementioned phosphorus (III) and phosphorus (I) compounds and the hydrogen sulfites are usually in larger quantities z. B. 0.5 to 10 wt .-% and in particular 1 to 8 wt .-%, based on the monomers to be polymerized. Also by the choice of the appropriate solvent can be influenced on the average molecular weight. Thus, the polymerization in the presence of diluents with benzylic or allyl N-atoms to a reduction of the average molecular weight by chain transfer.

The Polymerization of the monomers can be carried out by the customary polymerization processes done, including solution, precipitation, Suspension or bulk polymerization carried out. Is preferred the method of solution polymerization, d. H. the polymerization in solution or diluents.

Suitable solvents or diluents include both aprotic solvents, e.g. B. the aforementioned aromatics such as toluene, o-xylene, p-xylene, cumene, chlorobenzene, ethylbenzene, technical mixtures of alkylaromatics, aliphatic and cycloaliphatic compounds such as cyclohexane and technical Aliphatenmischungen, ketones such as acetone, cyclohexanone and methyl ethyl ketone, ethers such as tetrahydrofuran, dioxane, Diethyl ether, tert-butyl methyl ether, and C ₁ -C ₄ alkyl esters of aliphatic C ₁ -C ₄ carboxylic acids such as methyl acetate and ethyl acetate, furthermore erotic solvents such as glycols and glycol derivatives, polyalkylene glycols and derivatives thereof, C ₁ -C ₄ alkanols, eg , As n-propanol, n-butanol, isopropanol, ethanol or methanol, and water and mixtures of water with C ₁ -C ₄ -alkanols such. B. isopropanol / water mixtures. The copolymerization process according to the invention is preferably carried out in water or a mixture of water with up to 60% by weight of C ₁ -C ₄ -alkanols or glycols as solvent or diluent. Particular preference is given to using water as the sole solvent.

The Polymerization of the monomers M is preferred under a wide or complete Exclusion of oxygen, preferably in an inert gas stream, z. As a nitrogen stream, performed.

The Polymerization process of the monomers M can be carried out in the usual apparatus for polymerization carried out become. Which includes stirred tank, stirred tank cascades, Autoclaves, tube reactors and kneaders.

The Polymerization of the monomers M usually takes place at temperatures in the range of 0 to 300 ° C, preferably in the range of 40 to 120 ° C. The polymerization time is usually in the range of 0.5 h to 15 h and especially in the range of 2 until 6 h. The pressure prevailing in the polymerization is for success the polymerization of minor importance and is located in the Usually in the range of 800 mbar to 2 bar and often at ambient pressure. at Use more volatile solvent or volatile monomers The pressure can also be higher be.

Because of Further details of the polymerization process is given in EP-A 560602, EP-A 734359, EP-A 799807, EP-A 994290, WO 01/40337, WO 01/40338 and PCT / EP 2005/009466. The polymerization conditions described therein can in an analogous manner to the preparation of comb polymers of the invention be used.

at the monomers M2, M4 and M5 are known compounds, the predominantly commercially available are.

Some of the monomers M1 and M3 have already been described in the prior art, where the monomers M1 or M3, where n in group A is on average, have a number in the range from 10 to 300, in particular in the range from 20 to 200, especially in Is from 50 to 200 and more particularly in the range of 50 to 150 and in which at least 90 mol% of the repeating units Alk-O in the group A are CH ₂ CH ₂ O, are new and form a further subject of the present invention. Their preparation can be carried out in analogy to known methods of the prior art. With regard to the statistical and blockwise arrangement of different units Alk-O, what has been said previously for group A applies.

Preferred monomers M1, in which k in formula A is 1, can be obtained by esterification of monoethylenically unsaturated C ₃ -C ₈ -monocarboxylic acids or monoethylenically unsaturated C ₄ -C ₈ -dicarboxylic acids with alcohols of the formula HO- (alk-O) _n - YZ in which n, Alk, Y and Z have the abovementioned meanings, or by amidation of monoethylenically unsaturated C ₃ -C ₈ -monocarboxylic acids with amines of the formula NHR- (Alk-O) _n -YZ, where n, Alk, R, Y and Z have the meanings given above, are prepared. Instead of the C ₃ -C ₈ -monocarboxylic acids or C ₄ -C ₈ -dicarboxylic acids it is also possible to use ester- or amide-forming derivatives of these acids, in particular the anhydrides of the acids. Such methods are known in the art.

• a) Sauer katalysierte Veresterung von monoethylenisch ungesättigten C₃-C₈-Monocarbonsäuren bzw. C₄-C₈-Dicarbonsäuren mit Alkoholen der Formel HO-(Alk-O)_n-Y-Z, beispielsweise in Analogie zu den DE-A 2516933, EP-A 884290, EP-A 989108, EP-A 989109, WO 01/40337, WO 01/40338 und WO 02/50160 beschriebenen Verfahren;
• b) Umesterung von Mono- bzw. Di-C₁-C₄-alkylestern monoethylenisch ungesättigter C₃-C₈-Monocarbonsäuren bzw. C₄-C₈-Dicarbonsäuren mit Alkoholen der Formel HO-(Alk-O)_n-Y-Z in Gegenwart von basischen oder sauren Umesterungskatalysatoren in Analogie zu dem in DE-A 19602035, US 5,037,978 , EP-A 799807 beschriebenen Verfahren oder unter Enzym-Katalyse nach dem in EP-A 999229 beschriebenen Verfahren,
• c) Umsetzung von Anhydriden monoethylenisch ungesättigter C₃-C₈-Monocarbonsäuren bzw. C₄-C₈-Dicarbonsäuren mit Alkoholen der Formel HO-(Alk-O)_n-Y-Z, beispielsweise in Analogie zu dem in WO 01/74736 oder in der älteren Anmeldung PCT/EP 2005/009466 beschriebenen Verfahren, wobei abweichend von den dort beschriebenen Methoden auf den Zusatz einer Base in einigen Fällen verzichtet werden kann.

Thus, for example, the preparation of esters of monoethylenically unsaturated C ₃ -C ₈ monocarboxylic acids or C ₄ -C ₈ dicarboxylic acids with alcohols of the formula HO- (Alk-O) _n -YZ by

• a) acid catalyzed esterification of monoethylenically unsaturated C ₃ -C ₈ monocarboxylic acids or C ₄ -C ₈ -dicarboxylic acids with alcohols of the formula HO- (Alk-O) _n -YZ, for example in analogy to DE-A 2516933, EP-A 884290, EP-A 989108, EP-A 989109, WO 01 / 40337, WO 01/40338 and WO 02/50160;
• b) transesterification of mono- or di-C ₁ -C ₄ -alkyl esters of monoethylenically unsaturated C ₃ -C ₈ -monocarboxylic acids or C ₄ -C ₈ -dicarboxylic acids with alcohols of the formula HO- (alk-O) _n -YZ in Presence of basic or acidic transesterification catalysts in analogy to that in DE-A 19602035, US 5,037,978 , EP-A 799807 or under enzyme catalysis according to the method described in EP-A 999229,
• c) Reaction of anhydrides of monoethylenically unsaturated C ₃ -C ₈ -monocarboxylic acids or C ₄ -C ₈ -dicarboxylic acids with alcohols of the formula HO- (Alk-O) _n -YZ, for example in analogy to that described in WO 01/74736 or in US Pat the older application PCT / EP 2005/009466 described method, which deviates from the methods described therein on the addition of a base in some cases can be omitted.

The preparation of amides of monoethylenically unsaturated C ₃ -C ₈ monocarboxylic acids with amines of the formula HNR- (Alk-O) _n -YZ can be carried out in analogy to known amidation reactions by amidation of monoethylenically unsaturated C ₃ -C ₈ -monocarboxylic acids or of their amide-forming derivatives such as acid chlorides, acid anhydrides or C ₁ -C ₄ alkyl esters, carried out with amines.

The preparation of ethylenically unsaturated ethers or amines, ie monomers M1 with a group A, wherein k = 0, can be achieved by etherification or vinylation of alcohols of the formula HO- (Alk-O) _n -YZ or by alkenylation or enamine Bidlung of Amines of the formula HNR- (Alk-O) _n -YZ be carried out in analogy to standard methods of the prior art.

The monomers M3 can be prepared in analogy to the methods described here for the monomers M1. In particular, the preferred monomers M3 are prepared by reacting anhydrides of monoethylenically unsaturated C ₄ -C ₈ -dicarboxylic acids with alcohols of the formula HO- (Alk-O) _n -YZ under conditions which lead to a monoester formation.

According to a preferred embodiment of the invention, the preparation of the particularly preferred monomers M1 by reacting anhydrides of monoethylenically unsaturated C ₃ -C ₈ monocarboxylic acids, in particular of acrylic anhydride or methacrylic anhydride, with alcohols of the formula HO- (Alk-O) _n -YZ. This process, in contrast to the processes known from the prior art when using alcohols of the formula HO- (Alk-O) _n -YZ to particularly good yields and therefore constitutes a further subject of the invention.

in this connection it has proved to be advantageous, the anhydride equimolar or in a small surplus to use, preferably 10 mol%, often 9.5 mol%, preferably 9 mol%, in particular 8.5 mol%, and especially 8 mol%, based on Do not exceed 1 mole of alcohol is, d. H. the amount of anhydride is typically at most 1.095 Mol, preferably not more than 1.09 mol, especially not more as 1.085 mole and especially not more than 1.08 mole per mole of alcohol. Preferably, at least 1.005 mol, in particular at least 1.01 mol and more preferably at least 1.02 mol of anhydride per Mole of alcohol.

In an embodiment The invention involves the reaction of the anhydride with the alcohol in the absence of a base, especially if it is the nitrogen heterocycle Z is a basic residue. In another embodiment The invention involves the reaction of the anhydride with the alcohol in the presence of a base. Of these, bases are preferred which are in Alcohol at 90 ° C not or only slightly soluble is, d. H. the solubility the base in which alcohol is at 90 ° C not more than 10 g / L and especially not more than 5 g / L.

Examples of such bases include hydroxides, oxides, carbonates, and bicarbonates of monovalent or divalent metal cations, particularly elements of the first and second main groups of the periodic table, ie, Li ⁺ , Na ⁺ , K ⁺ , Rb ⁺ , Cs ⁺ , Be ²⁺ , Mg ²⁺ , Ca ²⁺ , Sr ²⁺ and Ba ²⁺ as well as mono- or divalent transition metal cations such as Ag ⁺ , Fe ²⁺ , Co ²⁺ , Ni ²⁺ , Cu ²⁺ , Zn ²⁺ , Cd ²⁺ , Sn ²⁺ , Pb ²⁺ , Ce ²⁺ . The hydroxides, oxides, carbonates and bicarbonates of cations of the alkali and alkaline earth metals and of Zn ²⁺ and in particular of Mg ²⁺ or Ca ²⁺ and particularly preferably of Na ⁺ or K ^{+ are} preferred. Preferred among these are the hydroxides and carbonates of these metal ions, in particular the alkali metal carbonates and alkali metal hydroxides and especially sodium carbonate, potassium carbonate, potassium hydroxide and sodium hydroxide. In particular, lithium hydroxide and lithium carbonate are also suitable. The base is preferably in an amount of 0.05 to 0.5 base equivalents and in particular in an amount of 0.1 to 0.4 base equivalents, based used on the alcohol, with larger amounts of base z. B. to 1 base equivalent usually not disadvantageous. It should be noted that in the case of hydroxides and bicarbonates, the base equivalents correspond to the molar equivalents used, whereas 1 molar equivalent of a carbonate or oxide corresponds in each case to 2 base equivalents.

The Reaction of the anhydride with the alcohol is preferably carried out at temperatures in the range of 0 and 150 ° C, in particular in the range from 20 to 130 ° C and more preferably in the Range of 50 and 100 ° C. The pressure prevailing in the implementation is responsible for the success of the reaction subordinate importance and is usually in the range of 800 mbar to 2 bar and often at ambient pressure. Preferably, the reaction is carried out in one inert gas atmosphere by. The reaction of the anhydride with the compound P can be carried out in all for Such reactions usual Equipment performed be, for. B. in a stirred tank, in stirred tank cascades, Autoclaves, tube reactors or kneaders.

The reaction of the anhydride with the alcohol is preferably carried out until a conversion of the alcohol used of at least 80%, in particular at least 90% and particularly preferably at least 95% is achieved. The reaction times required for this purpose will generally not exceed 5 hours and often times less than 4 hours. The conversion can be monitored by ¹ H-NMR spectroscopy of the reaction mixture, preferably in the presence of a strong acid such as trifluoroacetic acid.

The Reaction of the anhydride with the alcohol may be carried out in bulk, i. H. without Addition of solvents, or in inert solution or diluents carried out become. Inert solvents are usually aprotic compounds. To the inert solvents counting optionally halogenated aromatic hydrocarbons, such as toluene, o-xylene, p-xylene, cumene, chlorobenzene, ethylbenzene, technical mixtures of Alkylaromatics, aliphatic and cycloaliphatic hydrocarbons such as hexane, heptane, octane, isooctane, cyclohexane, cycloheptane, technical Aliphatenmischungen, continue ketones such as acetone, methyl ethyl ketone, Cyclohexanone, furthermore ethers, such as tetrahydrofuran, dioxane, diethyl ether, tert-butyl methyl ether, and mixtures of the aforementioned solvents such as For example, toluene / hexane. Preferably, without solvent or only with a lot small amounts of solvent, usually less than 10% by weight, based on the starting materials, d. H. in substance, worked.

It has proven to be beneficial when one considers the reaction of the anhydride with the alcohol in a reaction medium containing less than 0.2% by weight and in particular contains less than 1000 ppm of water (determined by Karl Fischer titration).

Of the Term "reaction medium" refers to the mixture of the reactants with the base and optionally used solvent and inhibitor. In the case of moisture-containing feeds has it proven to remove the water before the reaction, z. B. by distillation and particularly preferably by distillation with addition of an organic Solvent, that forms a low-boiling azeotrope with water. Examples of such solvent are the aforementioned aromatic solvents such as toluene, o-xylene, p-xylene, cumene, benzene, chlorobenzene, ethylbenzene and technical Aromatic mixtures, furthermore aliphatic and cycloaliphatic solvent such as hexane, heptane, cyclohexane and technical Aliphatenmischungen and mixtures of the aforementioned solvents.

to Implementation becomes common proceeding so that the reaction mixture containing the alcohol, the anhydride and the base and optionally solvent and optionally Inhibitor in a suitable reaction vessel at the above Temperatures brings to the reaction. Preferably, you put the alcohol and the base and optionally the solvent and gives this the anhydride. Preferably, the addition of the anhydride occurs at Reaction temperature.

Provided the feeds contain water, the water is preferably remove before adding the anhydride. For example, you can Proceed in such a way that alcohol and possibly the base and optionally the solvent in a reaction vessel, subsequently possibly existing moisture in the manner described above and then adding the anhydride, preferably at reaction temperature.

In addition, it has proven to avoid uncontrolled polymerization to carry out the reaction of the anhydride with the alcohol in the presence of a polymerization inhibitor. Suitable are the polymerization inhibitors known for such reactions, in particular phenols such as hydroquinone, hydroquinone monomethyl ether, especially sterically hindered phenols such as 2,6-di-tert-butylphenol or 2,6-di-tert-butyl-4-methylphenol, furthermore thiazines such as Phenothiazine or methylene blue, cerium (III) salts such as Cerium (III) acetate and nitroxides, in particular sterically hindered nitroxides, ie nitroxides of secondary amines, each of the C atoms, which are adjacent to the nitroxide group, carry 3 alkyl groups, each 2 of these alkyl groups, especially those which are not the same C atom are, with the nitrogen atom of the nitroxide or the carbon atom to which they are attached, form a saturated 5- or 6-membered ring, such as in 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO ) or 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl (OH-TEMPO), mixtures of the aforementioned inhibitors, mixtures of the aforementioned inhibitors with oxygen, for. In the form of air, and mixtures of mixtures of the aforementioned inhibitors with oxygen, e.g. B. in the form of air. Preferred inhibitors are the aforementioned sterically hindered nitroxides, cerium (III) compounds and sterically hindered phenols and mixtures thereof and mixtures of such inhibitors with oxygen and mixtures of mixtures of these inhibitors with oxygen, for. B. in the form of air. Particularly preferred are inhibitor systems comprising at least one sterically hindered nitroxide and another component selected from a sterically hindered phenol and a cerium (III) compound, and mixtures thereof with oxygen, e.g. B. in the form of air. The amount of inhibitor may be up to 2% by weight, based on the total amount of anhydride + alcohol. The inhibitors are advantageously used in amounts of from 10 ppm to 1000 ppm, based on the total amount of anhydride + alcohol. In the case of inhibitor mixtures, this information refers to the total amount of components except oxygen.

The reaction of the alcohol with the anhydride of a monoethylenically unsaturated C ₃ -C ₈ monocarboxylic acid naturally leads primarily to a mixture of the ester with the monoethylenically unsaturated C ₃ -C ₈ monocarboxylic acid used and optionally residues of excess anhydride and unreacted alcohol.

The excess anhydride however, does not usually make more than 10% by weight, and especially not more than 5% by weight of the original used amount of anhydride. It has proven itself, possibly existing Anhydride by reaction with water to destroy. The proportion of unreacted Alcohol is preferably not more than 10% by weight and in particular not more as 5 wt .-% of the amount of alcohol used.

For the separation of the alcohol from the monoethylenically unsaturated C ₃ -C ₈ monocarboxylic acid formed in the reaction, the latter can in principle by distillation or in any other way, for. B. by extraction of the acid remove. Also, one can isolate the ester, for. Example, by crystallization of the ester from an aqueous medium, wherein the acid and optionally present anhydride remains in the mother liquor. In general, however, one will make no isolation or separation of the ester. Rather, it is preferable to subject the mixture of esters with monoethylenically unsaturated C ₃ -C ₈ monocarboxylic acid, optionally with the addition of further monomers M2 and optionally further ethylenically unsaturated monomers M3, M4 and / or M5 directly to a radical copolymerization.

In analogous way you can also by esterification by the method a) or by transesterification according to the method b) prepared monomers M1 or M3 directly, d. H. without previous isolation or purification in the subsequent Use polymerization of the monomers M.

Provided the polymerization of the monomers M as solution polymerization in water carried out is, is for Many uses do not require removal of the water. Furthermore can be an isolation of the polymer obtainable according to the invention in more usual Manner performed be, for. B. by spray drying of the polymerization mixture. If the polymerization in a steam-volatile solvent or solvent mixture carried out, so you can use the solvent by introducing water vapor, whereby an aqueous solution or Dispersion of the comb polymer receives.

Prefers The comb polymers are recovered in the form of an aqueous dispersion or solution. Of the Solid content is preferably 10 to 80 wt .-%, in particular 30 to 65 wt .-%.

Another embodiment of the invention relates to comb polymers which are obtainable by the production process iii). Herein, a homo- or copolymer having a carbon backbone having carbon-free carboxylic groups or ester-forming derivatives of carboxyl groups, with alcohols of the formula HO- (Alk-O) _n -YZ or amines of the formula HNR- (Alk-O) _n - YZ implemented in the sense of a polymer-analogous reaction. A process for the polymer-analogous reaction of homopolymers or copolymers which have free carboxyl groups or ester-forming derivatives of carboxyl groups are known from the prior art, for example from US Pat US 5,840,114 . US 5,728,207 , WO 98/31643 and WO 01/72853. The processes described there can be carried out in an analogous manner to the preparation of the comb polymers according to the invention be used.

Examples of polymers having free carboxyl groups or ester-forming derivatives of free carboxyl groups, in particular anhydride groups, are homopolymers and copolymers of monoethylenically unsaturated C ₃ -C ₈ -monocarboxylic acids and / or C ₄ -C ₈ -dicarboxylic acids or their anhydrides, for example homo- and Copolymers of acrylic acid, methacrylic acid, maleic acid, maleic anhydride into consideration. These polymers may contain other monomers M2, e.g. B. sulfonic acid-carrying monomers such as vinyl sulfonic acid, acrylamidomethylpropanesulfonic acid, Methallylsulfonsäure or their alkali metal or ammonium salts, but also monomers M4 and / or M5, for example vinyl aromatic monomers or olefins, in copolymerized form.

• – 5 bis 100 Gew.-%, insbesondere 50 bis 100 Gew.-% wenigstens einer monoethylenisch ungesättigten C₃-C₈-Monocarbonsäure und/oder C₄-C₈-Dicarbonsäure bzw. deren Anhydride, insbesondere Acrylsäure, Methacrylsäure, Maleinsäure oder Maleinsäureanhydrid, oder deren Mischungen;
• – 0 bis 95 Gew.-%, insbesondere 0 bis 50 Gew.-% monoethylenisch ungesättigten Sulfonsäuren, wie Vinylsulfonsäure, Acrylamidomethylpropansulfonsäure, Methallylsulfonsäure und/oder deren Alkalimetall- oder Ammoniumsalze
• – und 0 bis 95 Gew.-%, insbesondere 0 bis 50 Gew.-% eines oder mehrerer Ester monoethylenisch ungesättigter C₃-C₈-Monocarbonsäuren oder C₄-C₈-Dicarbonsäuren, z. B. Ester der Acrylsäure, Methacrylsäure oder Maleinsäureester von einwertigen Alkoholen mit 1 bis 8 C-Atomen im Molekül.

Suitable carboxyl-containing polymers are, in particular, copolymers which consist of

• From 5 to 100 wt .-%, in particular 50 to 100 wt .-% of at least one monoethylenically unsaturated C ₃ -C ₈ monocarboxylic acid and / or C ₄ -C ₈ dicarboxylic acid or its anhydrides, in particular acrylic acid, methacrylic acid, maleic acid or Maleic anhydride, or mixtures thereof;
• 0 to 95% by weight, in particular 0 to 50% by weight, of monoethylenically unsaturated sulfonic acids, such as vinylsulfonic acid, acrylamidomethylpropanesulfonic acid, methallylsulfonic acid and / or their alkali metal or ammonium salts
• - And 0 to 95 wt .-%, in particular 0 to 50 wt .-% of one or more esters of monoethylenically unsaturated C ₃ -C ₈ monocarboxylic acids or C ₄ -C ₈ dicarboxylic acids, eg. As esters of acrylic acid, methacrylic acid or maleic acid esters of monohydric alcohols having 1 to 8 carbon atoms in the molecule.

Especially preferred carboxyl-containing polymers are homopolymers of acrylic acid and methacrylic acid, Copolymers of acrylic acid and methacrylic acid, Copolymers of methacrylic acid and vinylsulfonic acid, Copolymers of acrylic acid and maleic acid, Copolymers of methacrylic acid and maleic acid, Copolymers of acrylic acid and an ester of a monoethylenically unsaturated carboxylic acid, copolymers from methacrylic acid and an ester of a monoethylenically unsaturated carboxylic acid as well the alkali metal or ammonium salts of said copolymers.

Especially the carboxyl-containing polymers are preferred which by radical polymerization of the aforementioned monomers in the presence one of the aforementioned molecular weight regulators available, in particular those obtained by free-radical polymerization in aqueous solution in the presence of at least 4% by weight, based on that in the polymerization used monomers, a water-soluble sulfur compound available are in which the sulfur has the oxidation number +4. Such water-soluble Sulfur compounds are for. Sulfur dioxide, sulfurous acid, alkali metal, Alkaline earth metal and ammonium salts of sulphurous acid or the desulphurous acid, Sodium, potassium, calcium or ammonium formaldehyde sulfoxylate, Dialkyl sulfites or mixtures thereof. In particular, of these compounds Potassium, ammonium or calcium sulphite, sodium, potassium, calcium or ammonium disulphite, sodium, Potassium, calcium or ammonium hydrogen sulfite or mixtures thereof. For further details on the polymerization, reference is made to WO 01/72853 Referenced.

The Molar mass (number average) of these polymers is typically in the Range of 500 to 100,000, preferably in the range of 1000 to 50000. Particularly preferred are homopolymers of acrylic acid or methacrylic acid or copolymers of methacrylic acid and acrylic acid.

Specific examples of acid group-containing polymers (percentages are% by weight) are:
Polyacrylic acid with molecular weight 2000,
Polyacrylic acid of molecular weight 4000,
Polyacrylic acid with molecular weight 8000,
Polyacrylic acid with molecular weight 20000,
Copolymer of 70% acrylic acid and 30% maleic acid with molecular weight 70000,
Copolymer of 50% acrylic acid and 50% maleic acid with molecular weight 5000,
Copolymer of 70% methacrylic acid and 30% maleic acid with molecular weight 5000,
Copolymer of 70% acrylic acid and 30% methacrylic acid with molecular weight 10000,
Copolymer of 90% acrylic acid and 10% vinylsulfonic acid with molecular weight 10000,
Copolymer of 50% acrylic acid and 50% methacrylic acid with molecular weight 6000,
Copolymer of 20% acrylic acid and 80% methacrylic acid with molecular weight 5000,
Copolymer of 80% acrylic acid and 20% methacrylic acid with molecular weight 4000,
Terpolymer of 40% acrylic acid, 40% methacrylic acid and 20% maleic acid with molecular weight 5000.

The Molar weights given here are each the number average molecular weight.

The Reacting the carboxyl-containing polymers with the alcohols or amines can in the presence or even in the absence of catalysts respectively. For example, strong catalysts are used oxo like sulfuric acid, p-toluenesulfonic acid, benzenesulfonic, Methanesulfonic acid, phosphoric acid, phosphorous Acid or Hydrogen halides like hydrochloric acid. If one uses in the implementation of an acid acting as a catalyst, so the amounts are up to 10 wt .-%, preferably up to 5 wt .-%, based on the total amount of carboxyl group-containing polymers and Alcohols or amines.

The Weight ratio, in which the carboxyl group-containing polymer and the alcohols or amine can be between 99: 1 to 1:99 and is preferably in the range of 1: 1 to 5:95 and especially preferably in the range of 3: 7 to 1: 9 reacted.

The Implementation is carried out, for example, so that the aqueous solutions of the polymer optionally with a catalyst acting as Acid and added to the alcohol or amine and distilled off the water. The Distillation of the water from the mixture is usually carried out under Atmospheric pressure, can but also performed in a vacuum become. Often it is advantageous if during distillation a gas stream passed through the reaction mixture to the water and others volatile Remove shares faster. As a gas stream, air, nitrogen or steam. You can also do the water Remove under reduced pressure and in addition a gas flow through direct the reaction mixture. To get the water out of the reaction mixture to distill, you have to add energy to the mixture. suitable Apparatus for this are heatable stirred tanks, stirred tank with outboard Heat exchangers, stirred tank with internal heat exchangers, Thin film evaporator, Kneader or extruder. The evaporating water is over a vapor line removed from the reaction medium and in a heat exchanger condensed. It contains only small amounts of organic ingredients and can over a sewage plant be disposed of.

in the Connecting or simultaneously with the removal of water from the Reaction mixture enters a condensation reaction between the polymer and the alcohol or amine. The resulting water is also removed from the reaction medium. The implementation will be, for example carried out at temperatures in the range of 100 to 250 ° C. The temperature is correct depending on the reactor and the residence time. For example in a continuously operated extruder or thin-film evaporator condenses in which the residence time only a few seconds or minutes is, can be advantageously used temperatures between 150 C and 250 ° C. In discontinuously operated stirred kettles or kneaders you need for example, 1 to 15 hours and leads to condensation most of the time in the temperature range of 100 to 200 ° C by.

In A variant of the method can first be the carboxyl-containing Dehydrate polymers and the resulting powder or granules with the alcohol and / or Amine condense.

To the condensation is cooled, the reaction mixture and optionally in water solved. Aqueous solutions of the Reaction mixture can For example, be prepared so that you add water to the still 50 to 150 ° C warm reaction mass with stirring inflicts or that the liquid at temperatures of 50 to 150 ° C liquid reaction mass stirred in water. Usually is used so much water that a 20 to 95 wt .-%, preferably 30 to 50 wt .-% aqueous solution of the comb polymer. simultaneously or following the release optionally, the condensation product may be neutralized the remaining acid groups respectively. Neutralizing agents are alkali metal, alkaline earth metal oxides or hydroxides in solid form or in the form of from 10 to 50% by weight aqueous Solutions or slurries used in water. examples for suitable bases are lithium hydroxide, sodium hydroxide, calcium hydroxide, Calcium oxide, calcium hydroxide, magnesium oxide, magnesium hydroxide, Alumina and aluminum hydroxide. Depending on the degree of neutralization can the watery solutions the comb polymers have pH values in the range of 1 to 12.

To the condensation, the reaction mass can remain undiluted. On cooling It usually solidifies into a waxy mass that can easily be melted again. This results in variations for the Transport. For example, you can fill the reaction mass in barrels, from where the condensation product can be melted again. It can also be transported and stored in a molten state. But it is also possible aqueous solution manufacture and handle.

The anhydrous melt can also be mixed with inert powders, to free-flowing To get compacts. As an inert powder, for example diatomaceous earth, Silica gel, amorphous silica and / or amorphous silica.

The comb polymers according to the invention are ideal as additives (additives) for preparations mineral binder, in particular for the additive cementitious Preparations, such as concrete or mortar and are characterized in particular by superior properties in terms their liquefying Effect.

Under Cement is for example Portland cement, alumina cement or mixed Cement, such as pozzolanic cement, slag cement or to understand other types. In particular, the comb polymers according to the invention are suitable for cement mixtures, predominantly as cement components and in particular at least 80% by weight, based on the cement constituent, Portland cement included. The comb polymers of the invention are for this purpose usually in an amount of 0.01 to 10 wt .-%, preferably 0.05 to 3 wt .-%, based on the total weight of the cement in the cement preparation used.

The comb polymers according to the invention are also suitable in a special way for the addition of gypsum and gypsum-containing Preparations. The comb polymers of the invention are in this case usually in an amount of 0.01 to 10 wt .-%, preferably 0.05 to 3 wt .-%, based on the total weight of Plaster used in the plaster preparation.

The Comb polymers can in solid form or as aqueous solution to the ready-to-use preparation of the mineral binder are given. Also can be present in solid form comb polymer Formulate with the mineral binder and from there the ready to use Prepare cementitious preparations. Preferably, the comb polymer in liquid, d. H. dissolved emulsified or suspended form, for example in the form of polymerization, used in the preparation of the preparation, so when Anmachen.

The comb polymers according to the invention can also be used in combination with the known concrete flow improvers and / or concrete liquefiers based on naphthalene-formaldehyde condensate sulfonate, melamine-formaldehyde condensate sulfonate, phenolsulfonic acid-formaldehyde condensate, lignosulfonates and gluconates. Furthermore, together with celluloses, e.g. As alkyl or hydroxyalkyl celluloses, starches or starch derivatives are used. Also, they may be used in combination with high molecular weight polyethylene oxides (weight-average molecular weight M _w in the range of 100,000 to 8,000,000).

Farther can the preparation of the mineral binder conventional additives such as air entraining agents, Expansion agents, water repellents, retardants, setting accelerators, Antifreeze, sealants, pigments, corrosion inhibitors, Flow agents, Einpresshilfen, stabilizers or hollow microspheres are mixed. Such additives are described for example in EN 934.

Basically, the comb polymers according to the invention also be used together with film-forming polymers. These are to be understood as meaning those polymers whose glass transition temperature ≦ 65 ° C., preferably ≦ 50 ° C., especially preferably ≤ 25 ° C and completely particularly preferably ≦ 0 ° C is. Based Fox (T.G. Fox, Bull. Am. Phys. Soc. (Ser.II) 1, 1956, 123 established relationship between glass transition temperature of homopolymers and the glass transition temperature of copolymers, one skilled in the art will be able to find suitable polymers select.

Examples for suitable Polymers are the for for this purpose commercially available styrene-butadiene polymers and styrene-acrylates (see, for example, H. Lutz in D. Distler (Editor), "Aqueous Polymer Dispersions" Wiley-VCH, Weinheim 1999, chap. 10.3 and 10.4, pp. 230-252).

Furthermore, it is often advantageous to use the comb polymers according to the invention together with antifoams. This prevents that when preparing the ready-to-use mineral building materials too much air in the form of air pores are introduced into the concrete, which would reduce the strength of the hardened mineral building material. Suitable antifoaming agents include, in particular, polyalkylene oxide-based antifoam agents, trialkyl phosphates such as tributyl phosphate, and silicone-based antifoams. Also suitable are the ethoxylation products and the propoxylation products of alcohols having from 10 to 20 carbon atoms. Also suitable are the diesters of alkylene kolen or polyalkylene glycols and other conventional antifoams. Antifoams are usually used in amounts of from 0.05% to 10%, and preferably from 0.5% to 5% by weight, based on the comb polymers.

The Antifoam agents can be combined in various ways with the polymer. Is the polymer for example as aqueous solution before, the antifoaming agent may be added solid or dissolved to the solution of the comb polymer become. Is the defoamer in the aqueous polymer solution not soluble, then can Emulsifiers or protective colloids added to its stabilization become.

Lies the comb polymer in the form of a solid, as z. B. from a Spray drying or spray fluidized bed granulation shows, the antifoam agent may be mixed as a solid or during the spray drying process or spray granulation process be assembled together with the polymer.

The The following examples are intended to illustrate the invention.

analytics:

a) Determination of the K value:

The K values of the aqueous Sodium salt solutions the copolymers were prepared according to H. Fikentscher, Cellulose Chemistry, Vol. 13, 58-64 and 71-74 (1932) in aqueous solution at pH of 7, a temperature of 25 ° C and a polymer concentration of the sodium salt of the copolymer of 1% by weight.

b) Determination of the solids content:

The Determination by means of the MA30 analyzer from Satorius. For this purpose, in an aluminum dish, a defined amount of the sample Weighed out (about 0.5 to 1 g) and dried to constant weight at 90 ° C. The percentage solids (FG) is calculated as follows: FG = Weighing × 100 / Weighing [Wt .-%].

c) Molecular weight determination:

The Determination of number average and weight average molecular weight was carried out by gel permeation chromatography (= GPC) with aqueous Eluents.

The GPC was performed with a device combination from Agilent (1100 series). This includes: fumigators Model G 1322 A Isocratic pump Model G 1310 A autosampler Model G 1313 A column oven Model G 1316 A control module Model G 1323 B differential refractometer Model G 1362 A

When Eluent is 0.08 mol / L in the case of polymers dissolved in water TRIS buffer (pH = 7.0) in distilled water + 0.15 mol / L chloride ions from NaCl and HCl.

The Separation took place in a separation column combination instead of. The columns are used No. 787 and 788 (each 8 × 30 mm) from PSS with separating material GRAL BIO linear. The flow rate was 0.8 mL / min at a column temperature of 23 ° C.

The Calibration is carried out with polyethylene oxide standards from PPS Molecular weights of M = 194 - 1700000 [Mol / g].

d) Preparation of alcohols of the formula HO- (Alk-O) _n -YZ

Preparation Example 1: alcohol HO- (CH ₂ CH ₂ O) ₂₀ -CH ₂ CH ₂ - (morpholin-4-yl)

In a 1L pressure vessel with 2 propeller stirrers (diameter 30/50 mm) were 98.3 g of N- (2-hydroxyethyl) morpholine and 0.87 g of potassium hydroxide submitted. The kettle was evacuated to 9 mbar and 1 h at 80 ° C internal temperature dewatered. Then it was aerated with nitrogen, inertized to 0.5 bar and with stirring over a period of 5.7 h and an internal temperature of 120 ° C 660.8 g of ethylene oxide added. The batch was at 120 ° C Stirred for 1 h and cooled to room temperature and relaxed. Thereafter, at normal pressure was heated to 100 ° C, evacuated to 100 mbar and stripped with nitrogen at 100 mbar for 30 min.

Subsequently was ventilated again with nitrogen, cooled to <80 ° C and neutralized with 0.81 g of acetic acid. A total of 760 g of the alcohol having an OH number of 61.8 received.

Preparation Example 2: Alcohol HO- (CH ₂ CH ₂ O) ₁₁₂ -CH ₂ CH ₂ - (morpholin-4-yl)

It was the same as in Preparation Example 1, but were presented only 19.7 g of N- (2-hydroxyethyl) morpholine and a total of 740.0 Ethylene oxide metered in 6.6 h. 755 g of the alcohol were taken an OH number of 11.4.

Preparation Example 3: Alcohol HO- (CH ₂ CH ₂ O) ₂₀ -CH ₂ CH ₂ - (pyrrolidin-2-one-1-yl)

It was carried out as in Preparation Example 1, but 105.9 g N- (2-hydroxyethyl) pyrrolidin-2-one and a total of 660.8 Ethylene oxide metered in 5.7 h. 766 g of the alcohol were obtained with an OH number of 60.1.

e) Preparation of monomers M1:

Comparative Example 1) Preparation of methacrylic acid ester of methyl polyethylene glycol (M = 3000 g / mol)

In a 1 l glass reactor with anchor stirrer, Thermometer, gas inlet, reflux condenser and Dropping funnels were 601.2 g of methyl polyethylene glycol (M = 3000 g / mol), 190 mg of 2,6-di-tert-butyl-4-methylpenol, 19.0 mg of 4-hydroxy-N, N-2,2,6,6-tetramethylpiperidine-1-oxyl and 3.3 g of sodium carbonate (anhydrous). The mixture was while introducing air at 80 ° C heated. Then, 38.5 g of methacrylic anhydride were added and let 3 Hours at 80 ° C react. After dilution with 346.4 g of water and cooling At room temperature was about 970 g of an aqueous solution of the ester of methacrylic acid together with methacrylic acid in molar ratio 1: 1 with a solids content of 65% and a pH of 6.9.

Comparative Example 2) Preparation of methacrylic acid ester of methyl polyethylene glycol (M = 1000 g / mol)

In a 1 l glass reactor with anchor stirrer, Thermometer, gas inlet, reflux condenser and Dropping funnels were 350 g of methyl polyethylene glycol (M = 1000 g / mol), 0.315 g of 2,6-di-tert-butyl-4-methylpenol, 31 mg of 4-hydroxy-N, N-2,2,6,6-tetramethylpiperidine-1-oxyl and 5.56 g of sodium carbonate (anhydrous) submitted. The mixture was heated to 80 ° C while introducing air. Then 57.74 g of methacrylic anhydride were added and let 3 Hours at 80 ° C react. Thereafter, 225.4 g of water were added and allowed to reach room temperature cooling down. An aqueous solution was obtained solution the ester of methacrylic acid together with methacrylic acid in molar ratio 1: 1 with a solids content of 65%.

Example 1: Preparation of methacrylic acid ester of the alcohol from Preparation Example 1

It The procedure was as in Comparative Example 1, but were 50.0 g of the alcohol from Preparation Example 1 with 69.9 g of methacrylic anhydride (90%) in the presence of 0.035 g of 4-hydroxy-N, N-2,2,6,6-tetramethylpiperidine-1-oxyl and 0.35 g of 2,6-di-tert-butyl-4-methylphenol and in the absence implemented by sodium carbonate. After dilution with 118.0 g of water About 230 g of an aqueous solution of the ester in a mixture with methacrylic acid in a molar ratio of 1: 1 with a solids content of 65% and a pH of 6.8.

Example 2: Preparation of methacrylic acid ester of the alcohol from Preparation Example 2

The procedure was as in Comparative Example 1, but 625.7 g of the alcohol were from Herstel Example 2 with 28.4 g of methacrylic anhydride (90%) in the presence of 0.014 g of 4-hydroxy-N, N-2,2,6,6-tetramethylpiperidin-1-oxyl and 0.14 g of 2,6-di- tert-butyl-4-methylphenol and reacted in the absence of sodium carbonate. After dilution with 352.3 g of water, about 1 kg of an aqueous solution of the ester in a mixture with methacrylic acid in a molar ratio of 1: 1 with a solids content of 65% and a pH of 6.9.

Example 3: Production of methacrylic acid ester of the alcohol from Preparation Example 3

In a 1I stirred vessel with nitrogen inlet and water separators were 200.0 g of the alcohol from Preparation Example 3, 79.3 g of methacrylic acid, 3.4 g of p-toluenesulfonic acid, 0.15 g of phenothiazine and 55.9 g of toluene are introduced and stirred Nitrogen at 140 ° C Bath temperature heated up. Under reflux was esterified for 7 h and thereby separating the resulting reaction water. After cooling, received About 330 g of a toluene solution of the ester in a mixture with excess methacrylic acid in a molar ratio of 1: 3.3.

f) Preparation of the comb polymers of the invention

Example 4: Preparation of the polymer according to the invention 1

In a 1 l glass reactor with anchor stirrer, Thermometer, nitrogen inlet, toluene separator and several Feed vessels were Submitted 298.7 g of water and heated to 100 ° C. Under initiation of Nitrogen then refluxed and stirring at the same time starting the feeds 1 and 3 within 5 h, feed 2 in 5.25 h continuously with constant Addition rate added. It was registered with feed 1 Toluene continuously separated at the separator. To the copolymerization to complete let one go after Termination of feeds Polymerize for a further 1 hour, then cooled the reactor contents and neutralized with 25 wt .-% sodium hydroxide solution.

The resulting solution had a solids content of 34.1% by weight and a pH of 6.8. The K value of the polymer was 37.0.
Feed 1: 224.7 g of the ester from Example 3 (toluene solution).
Feed 2: 2.9 g of sodium peroxodisulfate dissolved in 39.1 g of water.
Feed 3: 17.0 g of 40% strength by weight aqueous sodium bisulfite solution.

Example 5: Preparation of the polymer according to the invention 2

The polymerization was carried out as in Example 4, to give 241.9 g of water and the feeds 1 and 2 had the following composition.
Feed 1: 366 g of the reaction mixture from Example 2 (65% by weight), 5.8 g of methacrylic acid and 0.4 g of mercaptoethanol.
Feed 2: 21.0 g of a 7.5% strength by weight solution of sodium peroxodisulfate in water.

Of the pH value and solids content of the resulting polymerization mixture and the K value of the polymer are given in Table 1.

Example 6: Preparation of the polymer according to the invention 3

The polymerization was carried out as in Example 4, to give 224.6 g of water and the feeds 1 and 2 had the following composition.
Feed 1: 341.5 g of the reaction mixture from Example 2 (65% by weight), 12.9 g of methacrylic acid and 1.0 g of mercaptoethanol.
Feed 2: 30.0 g of a 7.5% strength by weight solution of sodium peroxodisulfate in water.

Of the pH value and solids content of the resulting polymerization mixture and the K value of the polymer are given in Table 1.

Example 7: Preparation of the polymer according to the invention 4

The polymerization was carried out as in Example 4 to give 388.3 g of water and feeds 1 and 2 had the following composition.
Feed 1: 248.7 g of the reaction mixture from Example 2 (65% strength by weight), 69.8 g of the reaction mixture from Ver Example 2 (65% by weight), 22.7 g of methacrylic acid and 1.7 g of mercaptoethanol.
Feed 2: 42.0 g of a 7.5% strength by weight solution of sodium peroxodisulfate in water.

Of the pH value and solids content of the resulting polymerization mixture and the K value of the polymer are given in Table 1.

Example 8: Preparation of the polymer according to the invention 5

The polymerization was carried out as in Example 4, to give 279.8 g of water and the feeds 1 and 2 had the following composition.
Feed 1: 123.4 g of the reaction mixture from Example 2 (65 wt .-%), 89.1 g of the reaction mixture from Comparative Example 1 (65 wt .-%), 34.6 g of the reaction mixture from Comparative Example 2 (65 % by weight), 22.7 g of methacrylic acid and 0.7 g of mercaptoethanol.
Feed 2: 25.7 g of a 7.5% strength by weight solution of sodium peroxodisulfate in water.

The pH and solids content of the resulting polymerization mixture and the K value of the polymer are shown in Table 1. Table 1:

g) Determination of the liquefying Effect of the comb polymers according to the invention 1 to 5

Apparatus:

• Two 300 ml plastic cups and a stirring motor with propeller stirrer. For the evaluation the truncated cone test specimen (inner diameter Base 3.5 cm / top 2 cm, height 6 cm), a glass plate and a 5 mm wide spatula.

Approach:

• 0.20 g of polymer (calculated at 100% by weight)
• 36.00 g of demineralised water (including water content of the respective polymer solution)
• 100.00 g cement CEM I 32.5 R (HeidelbergCement, Leimen plant)

Method:

The Weigh the cement into one beaker and the second with the polymer Dilute the specified amount of water. The cement to the diluted polymer solution stir and stir at 500 rpm for 1 min. The modified cement paste Let it rest for 3 minutes, then Stir for 15 s and fill in the truncated cone within 45 s. With the spatula 2x lateral and vent 5x vertically, possibly refill and smooth it out. The test specimen exactly 5 minutes after the beginning of the mixture lift off and let drip off for 10 seconds. The horizontal and measure the vertical diameter of the cement paste cake and from both readings to form the mean.

The following measured values were obtained:

The Results show that the polymers according to the invention are good to very good good liquefaction effect show in the cement paste.

Claims (25)

Use of comb polymers having a carbon backbone, the polyether groups of the formula A. * -U- (C (O)) _k -X- (Alk-O) _n -YZ A wherein * indicates the binding site to the carbon backbone of the comb polymer, U is a chemical bond or an alkylene group of 1 to 8 carbon atoms, X is oxygen or a group NR, k is 0 or 1, n is an integer whose Alk, is C ₂ -C ₄ alkylene, wherein Alk may be the same or different within the group (Alk-O) _n , Y is a linear or branched alkylene group with, based on the comb polymer in the range of 5 to 300 Z is a nitrogen-bonded 5- to 10-membered nitrogen heterocycle having as ring members, in addition to the nitrogen atom and in addition to carbon atoms, 1, 2 or 3 additional heteroatoms selected from May have oxygen, nitrogen and sulfur, wherein the nitrogen ring members may have a group R ', and wherein 1 or 2 carbon ring members may be present as a carbonyl group, R is hydrogen, C ₁ -C ₄ -Alkyl or benzyl, and R 'is hydrogen, C ₁ -C ₄ -alkyl or benzyl; and functional groups B, which are present at pH> 12 in the form of anionic groups, and their salts as additives in preparations containing a mineral binder. Use according to claim 1, wherein on average at least 50 mol% of the units Alk-O in the group (Alk-O) _{n are} CH ₂ -CH ₂ -O. Use according to one of the preceding claims, wherein Z in formula A for a 5- or 6-membered nitrogen heterocycle which is adjacent the nitrogen atom bonded to Y and carbon ring members selected from O, S, N and a group NR ring member and / or a Having carbonyl group as a ring member, wherein R is hydrogen or methyl. Use according to claim 3, wherein Z in formula A under Pyrrolidon-1-yl, morpholin-4-yl, piperazin-1-yl, piperidone-1-yl, Morpholin-2-one-4-yl, morpholin-3-one-4-yl, piperazin-1-yl, 4-methylpiperazin-1-yl, Imidazolin-2-one-1-yl, 3-methylimidazolin-2-one-1-yl and imidzol-1-yl selected is. Use according to one of the preceding claims, wherein on average at least every 4th carbon atom of the polymer backbone of the comb polymer carries a group A or a group B. Use according to one of the preceding claims, wherein the group B are carboxyl groups. Use according to any one of the preceding claims, wherein the comb polymer additionally comprises groups of formula C: * -U '- (C (O)) _p -X "- (Alk" -O) _q -R ^a C wherein U 'is a chemical bond or an alkylene group having 1 to 8 C atoms, X '' is oxygen or a group NR in which R is hydrogen or C ₁ -C ₄ -alkyl, p is 0 or 1, Alk '' is C ₂ -C ₄ -alkylene, wherein Alk '' within the group (Alk '' - O) _{q may be the} same or different, q is an integer whose mean value, based on the comb polymer in the range of 2 to 300, R ^{a is} selected from hydrogen, C ₁ -C ₁₀ alkyl , C ₁ -C ₁₀ alkylcarbonyl, benzyl or benzoyl. Use according to one of the preceding claims, wherein the comb polymer available is by copolymerization of ethylenically unsaturated Monomers M, comprising a) neutral monoethylenically unsaturated monomers M1, which have one or two groups of formula A, and b) monoethylenically unsaturated Monomers M2 which have one or two functional groups B, or by Homo- or copolymerization of ethylenically unsaturated monomers M comprising a) monoethylenically unsaturated Monomers M3, which is a group of formula A and a functional Group B, and optionally b) monoethylenically unsaturated monomers M2, which have one or two functional group B. Use according to claim 8, wherein the monomers M1 are selected from the esters of monoethylenically unsaturated C ₃ -C ₈ -monocarboxylic acids and diesters of monoethylenically unsaturated C ₄ -C ₈ -dicarboxylic acids with alcohols of the formula HO- (Alk-O) _n -YZ, in which n, Alk, Y and Z have the meanings given above, and the amides of monoethylenically unsaturated C ₃ -C ₈ monocarboxylic acids with amines of the formula NHR- (Alk-O) _n -YZ, where n, Alk, R, Y and Z have the meanings mentioned above. Use according to claim 8, wherein the monomers M3 are selected from the monoesters of monoethylenically unsaturated C ₄ -C ₈ -dicarboxylic acids with alcohols of the formula HO- (Alk-O) _n -YZ, where n, Alk, Y and Z have the abovementioned meanings exhibit. Use according to claim 8, 9 or 10, wherein the monomers M2 are selected from monoethylenically unsaturated C ₃ -C ₈ -monocarboxylic acids and monoethylenically unsaturated C ₄ -C ₈ -dicarboxylic acids. Use according to any one of claims 8 to 11, wherein the copolymerization the monomer M is carried out in the presence of a molecular weight regulator. Use according to any one of claims 1 to 7, wherein the comb polymer is obtainable by polymer-analogous reaction of homo- or copolymers with a carbon backbone having free carboxyl groups or ester-forming derivatives of carboxyl groups, with alcohols of the formula HO- (Alk-O) _n -YZ or amines of the formula HNR- (Alk-O) _n -YZ in which n, Alk, R, Y and Z have the abovementioned meanings. Use according to one of the preceding claims, wherein the mineral binder to at least 90% cement, gypsum or a mixture of cement with gypsum. Composition comprising at least one mineral Binder and at least comb polymer according to one of the preceding Claims. Comb polymers having a carbon backbone, the polyether groups of the formula A * -U- (C (O)) _k -X- (Alk-O) _n -YZ A wherein * indicates the binding site to the carbon backbone of the comb polymer, U is a chemical bond or an alkylene group of 1 to 8 carbon atoms, X is oxygen or a group NR, k is 0 or 1, n is an integer whose Alk, is C ₂ -C ₄ alkylene, wherein Alk within the group (Alk-O) _{n may be the} same or different, Y is a linear or branched alkylene group with, based on the comb polymer in the range of 11 to 300 Z is a nitrogen-bonded 5- to 10-membered nitrogen heterocycle, which as ring members, in addition to the nitrogen atom and in addition to carbon atoms, 1, 2 or 3 additional heteroatoms selected un oxygen, nitrogen and sulfur, wherein the nitrogen ring members may have a group R ', and wherein 1 or 2 carbon ring members may be present as a carbonyl group, R is hydrogen, C ₁ -C ₄ alkyl or benzyl, and R' is hydrogen C ₁ -C ₄ alkyl or benzyl; and functional groups B which are present in the form of anionic groups at pH> 12, with an average of at least 90 mol% of the units Alk-O in the group (Alk-O) _{n representing} CH ₂ -CH ₂ -O, and the salts of the comb polymers. A comb polymer according to any one of claims 16, wherein Z in formula A for one 5- or 6-membered Nitrogen heterocycle which is adjacent to the nitrogen atom attached to Y. and carbon ring members include O, S, N and a group NR selected Ring member and / or a carbonyl group as a ring member, wherein R for hydrogen or methyl. A comb polymer according to claim 17, wherein Z is in formula A is pyrrolidone-1-yl, morpholin-4-yl, piperazin-1-yl, piperidone-1-yl, Morpholin-2-one-4-yl, morpholin-3-one-4-yl, piperazin-1-yl, 4-methylpiperazin-1-yl, Imidazolin-2-one-1-yl, 3-methylimidazolin-2-one-1-yl and imidzol-1-yl selected is. A comb polymer according to any one of claims 16 to 18, wherein in the middle at least every 4th carbon atom of the polymer backbone of the comb polymer Carries group A or group B. A comb polymer according to any one of claims 16 to 19, wherein the group B are carboxyl groups. A comb polymer according to any one of claims 16 to 20, which additionally has groups of the formula C: * -U '- (C (O)) _p X "- (Alk" -O) _q -R ^a C wherein U 'is a chemical bond or an alkylene group having 1 to 8 C atoms, X''is oxygen or a group NR in which R is hydrogen or C ₁ -C ₄ alkyl, p is 0 or 1, Alk '' is C ₂ -C ₄ -alkylene, wherein Alk '' within the group (Alk '' - O) _{q may be the} same or different, q is an integer whose mean value, based on the comb polymer in the range of 2 to 300, R ^{a is} selected from hydrogen, C ₁ -C ₁₀ alkyl, C ₁ -C ₁₀ alkylcarbonyl, benzyl or benzoyl. A comb polymer according to any one of claims 16 to 21 which is obtainable by Copolymerization of ethylenically unsaturated monomers M comprising a) neutral monoethylenically unsaturated Monomers M1, which have one or two groups of the formula A, and b) monoethylenically unsaturated Monomers M2 which have one or two functional groups B, or by Homo- or copolymerization of ethylenically unsaturated monomers M comprising a) monoethylenically unsaturated Monomers M3, which is a group of formula A and a functional Group B, and optionally b) monoethylenically unsaturated monomers M2, which have one or two functional group B. A comb polymer according to claim 22, wherein the copolymerization the monomer M is carried out in the presence of a molecular weight regulator. A comb polymer according to any one of claims 16 to 21 which is obtainable by polymer-analogous reaction of homopolymers or copolymers having a carbon backbone which have free carboxyl groups or ester-forming derivatives of carboxyl groups, with alcohols of the formula HO- (alk-O) _n -YZ or amines of the formula HNR- (Alk-O) _n -YZ in which n, Alk, R, Y and Z have the meanings mentioned in claim 16. Comb polymers in the form of an aqueous solution of the alkali metal salts.